JPH0359087A - Tacky, water-swelling material for stopping water - Google Patents

Abstract

PURPOSE:To obtain the title material improved in workability, capability of filling interstices, and the water stopping effect by molding and vulcanizing a mixture of a butyl rubber, a highly water-absorptive resin, an inorganic water absorbent, a tackifier, a plasticizer, and a vulcanizing agent. CONSTITUTION:100 pts.wt. butyl rubber (e.g. a brominated butyl rubber having a degree of unsaturation of 0.3-3.0mol%) is mixed with 1-50 pts.wt. highly water- absorptive resin (e.g. PVA), 30-200 pts.wt. inorganic water absorbent (e.g. bentonite), 10-50 pts.wt. tackifier (e.g. polyterpene), 20-50 pts.wt. plasticizer (e.g. naphthenic process oil), 0.1-5 pts.wt. vulcanizing agent (e.g. tetramethylthiuram disulfide), if necessary, at most 5 pts.wt. vulcanization accelerator (e.g. 2- mercaptoimidazoline) and an age resister, a filler, a coloring agent, etc. The mixture thus obtained is molded and vulcanized to give the title material having a tensile strength of 30kgf/cm<2> or lower, a 100% modulus of 1kgf/cm<2> or higher, an elongation at break of 300% or greater, and a degree of swelling of 1.5 to 5.0.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel self-adhesive water-swelling wood. More specifically, the present invention relates to an adhesive water-swelling lumber that has improved workability and has a high water-stopping effect.

Conventional technology Stoppers are widely used in civil engineering and construction work to stop water leaks by filling them into cracks, fissures, and gaps in mortar and concrete construction and water pipe connections. ing.

Conventionally, fully vulcanized water-stopping materials have been mainly used as such stoppers, but this type has high tensile strength (Tb) and high compression resilience, so it can be used for joints with complex shapes. When used in joints of concrete products with relatively rough surfaces, such as parts and corners of concrete products, a considerable amount of clamping force is required to fill in the gaps, resulting in poor workability. Improvements are desired. It's here. In addition, there are also known materials made from easily deformable water-resistant materials such as rubber, plastic, and bitumen, but these materials tend to lose impact resilience or creep due to long-term use, resulting in the gap becoming smaller. It has the disadvantage that it cannot respond to changes and its water-stopping effect is insufficient. In addition, water-swellable vulcanized rubber-type stoppers have been proposed, but the initial water-stopping effect largely depends on the compressive rebound force of the adhesive and rubber.
Improvements in workability are desired.

On the other hand, adhesive butyl rubber-based fasteners have been widely used as fasteners for gap light beams, but because of their large compression set and low restoring force, there is a risk of water leakage. Water-swellable butyl rubber-based fasteners have a fundamental drawback in that, because they are unvulcanized, the fasteners cannot withstand the expansion pressure and collapse after water absorption and expansion.

Problems to be Solved by the Invention The present invention overcomes the drawbacks of the conventional adhesive water expansion prevention lumber, and has excellent adhesiveness, relatively low compression resilience, and low gap light resistance during construction. Adhesive water-swelling lumber with excellent properties, such as exhibiting a water-stopping effect with the contact pressure caused by water expansion even when gaps are separated after construction, and having a base material strength that does not collapse even after water absorption and expansion. It was made for the purpose of providing.

Means for Solving the Problems The present inventors have conducted various studies in order to develop an adhesive water-swellable fastener having the above-mentioned preferable properties. It was discovered that the purpose could be achieved by molding the blended mixture and then vulcanizing it, and based on this knowledge, the present invention was completed.

That is, the present invention includes (A) 10 parts by weight of butyl rubber, (B) 1 to 50 parts by weight of super absorbent resin, (C) 30 to 200 parts by weight of inorganic water absorbing agent, and (D) tackifier. 10
~50 parts by weight, (E) 30 to 200 parts by weight of plasticizer, and (
F) A vulcanized molded product of a mixture containing 0.1 to 5 parts by weight of a vulcanizing agent, and having a tensile strength (Tb) of 30 and 9 f/cr.
tr” or less, 100% modulus 1 kgf/cm”
or more, elongation at break (Eb) of 300% or more, expansion degree (S
) 1.5 to 5.0.
# Provided by Zhang Zhang Shui Wood.

Here, the degree of swelling (S) is defined by the formula (t; W is the weight in a dry state; W is the weight after 3 weeks of immersion in tap water).

The present invention will be explained in detail below.

In the present invention, the butyl rubber used as the Iffi component (A) includes, for example, butyl rubber, especially those having an unsaturation degree of 0.3 to 3.0 mol%, and halogenated butyl rubbers such as chlorinated butyl rubber and brominated butyl rubber. Among them, polyisobutylene with an unsaturation degree of 0.1 to 3.0 mol%, a halogen content of 0.33 to 3.0% by weight, and a polyisobutylene with a viscosity average molecular weight of 50,000 to 2,500,000 are mentioned. Brominated butyl rubber with high reactivity is preferred.

In the present invention, examples of the superabsorbent resin used as component (B) include polyacrylic acid, modified polyvinyl alcohol, vinyl alcohol-acrylic acid copolymer,
Examples include olefin-maleic anhydride systems. This CB) ingredient! It is usually blended in a proportion of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of component (A).

If this mixing ratio is too small, the degree of expansion will be insufficient or the expansion time will be prolonged, resulting in a deterioration of the water-stopping effect. If it is too large, cracks in the concrete may occur due to collapse of the base material or extrusion of the backfill material. cannot be avoided.

In the present invention, the inorganic water-absorbing agent used as component (C) is not particularly limited as long as it is an inorganic material that absorbs water and expands. Examples include silicic acids such as salts and bentonites whose main component is montmorillonite. This <c> component is usually 3 parts by weight per 100 parts by weight of component (A).
It is blended in a proportion ranging from 0 to 200 parts by weight, preferably from 50 to 150 parts.

If this ratio is too small, the degree of expansion will be insufficient, or it will take a long time to expand, which will deteriorate the water-stopping effect. If it is too large, the base material will collapse or harden during expansion. , it is inevitable that the workability will deteriorate.

In the present invention, examples of the tackifier used as component (D) include petroleum resins such as aliphatic, aromatic, alicyclic, copolymerized, and hydrogenated, and terbenes such as polyterpene and terpene phenol resin. xylene resins such as xylene resins, modified xylene resins, 7-enol resins such as alkylphenol resins and modified phenol resins, rosin resins such as coumaron-indene resins, rosins, and modified rosins,
Examples include shellac, dammar, copal, polybutene, polyisobutylene, liquid polyglobulene, and liquid polybutadiene. This (D) Iffi is (A)
The amount is usually 10 to 50 parts by weight, preferably 15 to 40 parts by weight, per 100 parts by weight of the components. If this blending ratio is too small, the adhesion will be insufficient and the filling ability for the adherend will be reduced. If it is too large, the surface will become hydrophobic, the degree of swelling will decrease, and the water-stopping effect will deteriorate. I can't escape it.

In the present invention, the plasticizers used as component (E) include mineral oils such as paraffinic, naphthenic, and aromatic phthalic acid plasticizers, phosphate ester plasticizers, adipate plasticizers, and sebacate plasticizers. agents, stearic acid, palmitic acid, castor oil, cottonseed oil, rapeseed oil, paraffin, chlorinated paraffin, etc. This (E)JR
The amount is usually 30 to 20 parts per 100 parts by weight of (A) * min.
0 parts by weight, preferably in the range of 50-150 parts by weight.

If this mixing ratio is too small, the base material will become hard, resulting in a decrease in the degree of expansion and deterioration of workability; if it is too large, the base material will become soft, leading to collapse of the base material after expansion. Become.

In the present invention, examples of the vulcanizing agent used as component (F) include sulfur, modified phenolic resins such as methylolated alkylphenol resins and brominated alkylphenol resins, and thiurams such as tetramethylthiuram disulfide and tetramethylthiuram monosulfide. can be mentioned. This vulcanizing agent is blended in a ratio of usually 0.01 to 5 parts by weight, preferably 0.3 to 2.0 parts by weight, per 100 parts by weight of component (A). If this blending ratio is too small, the vulcanized density will be low and the strength of the base material will be lowered, so that the base material will be more likely to collapse after water absorption and expansion, and if it is too large, bloom will occur, which is undesirable.

This vulcanizing agent is preferably used together with a vulcanization accelerator, and examples of the vulcanization accelerator include thiourea compounds such as 2-mercaptoimidacillin, mercaptobenzothiazole, and dibenzothiazyl disulfide. Examples include thiazole compounds such as, zinc dimethyldithiocarbamate, dithiocarbamate compounds such as copper dimethyldithiocarbamate, etc. These vary depending on the type of vulcanizing agent, etc., but (A) gt 100 parts by weight It is usually used in a proportion of 5 parts by weight or less, preferably 0.5 to 3 parts by weight.

In addition to the above-mentioned essential components, the mixture used in the present invention may optionally contain various additive components that are conventionally used in anchoring materials, as necessary, within a range that does not impair the purpose of the present invention. I can do it.

Examples of the additive components include anti-aging agents, fillers,
Colorants, pigments, processing aids, etc. may be mentioned.

Examples of the anti-aging agent include amines and phenols.

Examples of the filler include calcium carbonate, zinc white, hard clay, and carbon black.

The adhesive water-swellable stopper of the present invention is produced by sufficiently kneading the above-mentioned components using a pressurized kneading machine, and then molding the mixture.
Then, by vulcanization, tensile strength (Tb) 30 k
gt/cta” or less, 100%-t-sh57.l
kgf/C- or more, elongation at break (Eb) 300% or more,
It is manufactured by having a physical property of expansion degree (S) of 1.5 to 5.0. This molding method is generally a method conventionally used for molding a stopper, such as an extrusion molding method or a press molding method.

Effects of the Invention The adhesive water-swellable lumber of the present invention has excellent adhesiveness, relatively low compression resilience, and excellent gap brightness during construction.
It has excellent performance, such as exhibiting a water-stopping effect due to the contact pressure caused by water expansion even when gaps are separated from each other after construction, and has a base material strength that does not collapse even after water absorption and expansion, and excellent workability.

Therefore, the adhesive water expansion preventing lumber of the present invention can be used, for example, in civil engineering and construction work, on joint surfaces of shield tunnels and shield segments, joint parts of secondary concrete products such as hume pipes and prefabricated culvert boxes, and on joints of concrete secondary products such as hume pipes and prefabricated culvert boxes. Construction joint, U7 reum,
It can be suitably used as a material for gap light in the joints of secondary steel products such as corrugated pipes, as a material for various repairs, or as a water retaining material for agriculture, forestry, and horticulture.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, the types of various compounding agents used in Examples and Comparative Examples are shown on the skin surface.

Example 1 Part part by weight Butyl rubber (a) 100 Super water absorbent resin
20 Inorganic water absorbing agent
80 tackifier
20 Plasticizer 80 Vulcanizing agent (a) 2 Vulcanization accelerator
l filler
More than 100 components were blended and thoroughly kneaded for 30 minutes using a pressure kneader to obtain a butyl rubber compound.

Next, this was extruded using an 160IIll extruder at a screw rotation speed of 40 rprn and a die temperature of 80° C., and then vulcanized at 170° C. for 8 minutes to prepare a sample. This sample has a tensile strength of 19. Obn/c1.10
0% modulus 2.5hyf/car”, elongation at break 1
It had an expansion rate of 200% and a degree of expansion of 2.5, maintained its shape even when expanded, and did not collapse.

Example 2 1. Butyl rubber (2) 50. Butyl rubber (3) 50. Super water absorbent resin 40. Inorganic water absorbing agent 3.0 Tackifier
25 Plasticizer
75 Vulcanizing agent (A) 1.5 Vulcanizing agent (B) 0.8 Filler 80 or more components were blended and the compound obtained in the same manner as in Example 1 was extruded and molded at 170°C for 10 minutes. A sample was prepared by vulcanization. This sample has a tensile strength of 18.0 kgf/cm", 1
It had a modulus of 2-Okgf/crn'', an elongation at break of 1350%, and a degree of expansion of 4.2, and maintained its shape even during expansion without collapsing.

Example 3 Butyl rubber (c) 100 Elastomer (EPDM) 80
Super water absorbent resin 40 Inorganic water absorbing agent 60 Tackifier
50 plasticizer
120 vulcanizing agent (a)
2. Vulcanizing agent (B) 1. Filler More than 100 components were blended, and a compound obtained in the same manner as in Example 1 was extruded and vulcanized at 170° C. for 5 minutes to prepare a sample.

This sample has a tensile strength of 25.0&gf/cta”, 1
It had a 00% modulus of 2.2 kgf/C11'', an elongation at break of 950%, and a degree of expansion of 1.7, and maintained its shape during expansion without collapsing.

Example 4
Butyl rubber (c) 100 Super water absorbent resin IO inorganic water absorbing agent 120 Polybutene (tackifier) 10 Plasticizer
100 vulcanizing agent (a)
1 Vulcanizing agent (b)
l Filling agent 70
The above components were blended, a compound obtained in the same manner as in Example 1 was extrusion molded, and the compound was vulcanized at 170° C. for 10 minutes to prepare a sample. This sample had a tensile strength of L5. Obgf/
cry”, 100% modulus 1.3kgf/crx
It had an elongation at break of 1410% and a degree of expansion of 2.2, and maintained its shape even when expanded, without collapsing.

Example 5 Components Butyl rubber (c) Butyl rubber (recycled butyl rubber) Super water-absorbing resin Inorganic water absorbent Tackifier Plasticizer Vulcanizing agent (A) Vulcanizing agent (B) Filler Each of the above components is blended Then, in the same manner as in Example 1, the obtained compound was extruded and vulcanized at 170° C. for 0 minutes to prepare a sample. This sample had a tensile strength of 16. OJgf
/cttt”, 100% modulus 1.-8&gf/
am”, elongation at break 1150%, expansion degree 2.8,
It maintained its shape even when expanded and did not collapse.

Comparative example 1 (SBR-based fully vulcanized type) Weight part S B R
100 Plasticizer 7 Vulcanizing agent (a) 2 Vulcanization accelerator
3 stearic acid
l filler
A sample was prepared by blending 70 or more components, extruding the obtained compound in the same manner as in Example 1, and vulcanizing it at 170°C for 10 minutes. This sample has a tensile strength of 185J2
gf/cm”%100% Modulus 15ker/cm
``Elongation at break 650%, expansion degree 1, no expansion, physical force f
To f/j; Purple ~<F/su-1. Ze-Comparative Example 2 (
Chloroprene-based fully vulcanized) ingredients
Part by weight Chloroprene rubber
100 super absorbent resin 60
Magnesium oxide 4 Zinc* (filler) 5 Plasticizer
7 Vulcanizing agent (b)
l Stearin W11 (anti-aging agent) Two or more components were blended and obtained in the same manner as in Example 1; the compound was extruded and heated to 170'C! A sample was prepared by vulcanizing for 1'lO minutes. This sample had a tensile strength of 55 kef
/ cm”, 100% modulus 9 kgf/ crn
", it had an elongation at break of 670% and a degree of expansion of 6.1, and although it maintained its shape even when expanded and did not collapse, it had hard physical properties and poor workability.

Comparative example 3 (unvulcanized adhesive butyl rubber type)
Kobutyl Mango Rubber (I) 100 Polybutene (tackifier) 100 Tackifier 1° Calcium carbonate (filler) 150 Carbon black (filler) 30 The above components were blended and obtained in the same manner as in Example 1. Samples were prepared by extrusion molding the compound.

This sample has a tensile strength of 0.57 kgf/c++'', 10
0% modulus 0.5 kyf/cra'', elongation at break 1600%, and degree of expansion 1, which did not expand.

Comparative Example 4 (unvulcanized adhesive water-swellable butyl rubber type) Parts by weight Butyl rubber (a) 100 Super water-absorbing resin 40 Inorganic water-absorbing agent 50 Tackifier
A sample was prepared by blending the following components: 10 polybutene (tackifier) 100 fillers (calcium carbonate, carbon black) 120 or more, and extrusion molding the compound obtained in the same manner as in Example 1.

This sample has a tensile strength of 0.52&9f/cm”, 100
% modulus was 0.48 kef/crs'', elongation at break was 1550%, and because it was an unvulcanized type, it collapsed during the expansion test.

Comparative Example 5 (partially vulcanized rubber type) Partially vulcanized butyl rubber (ESCOLANT-10) 100 Super water absorbent resin 30 Inorganic water absorbing agent 40 Tackifier
A sample was prepared by blending each of the following components: lO polybutene (tackifier): 50% filler (calcium carbonate, carbon black): 150% or more, and a compound obtained in the same manner as in Example 1 was extruded.

This sample has a tensile strength of 7.0 kef/cyx”, 100
% modulus 4.4 to 9f/cm”, elongation at break 79
0%, and because it was not post-vulcanized, it collapsed when it expanded upon water absorption.

Claims (1)

[Claims] 1 (A) 100 parts by weight of butyl rubber, (B) 1 to 50 parts by weight of super absorbent resin, (C) 30 to 50 parts by weight of inorganic water absorbing agent
200 parts by weight, (D) 10 to 50 parts by weight of tackifier, (
E) 30 to 200 parts by weight of plasticizer and (F) 0.1 vulcanizing agent
A vulcanized molded product of a mixture containing ~5 parts by weight, and a tensile strength (Tb) of 30 kgf/cm^2 or less, 100
% modulus 1 kgf/cm^2 or more, elongation at break (E
b) A self-adhesive water-swellable waterstop material having a swelling degree (S) of 300% or more and a swelling degree (S) of 1.5 to 5.0.